JP5757947B2 - Ester of 2,5-furandicarboxylic acid and isomer decanol and use thereof - Google Patents

Description

  The present invention relates to a mixture of esters of 2,5-furandicarboxylic acid (FDCA) and a mixture of C10 alcohols, in particular branched decanols. Similarly, the invention relates to the preparation of such esters or mixtures and the use of said esters or mixtures as plasticizers for polymers such as polyvinyl chloride.

  Polyvinyl chloride (PVC) is one of the most economically important polymers. Widely used as hard PVC as well as soft PVC.

For the production of soft PVC, plasticizers are added to PVC, in most cases phthalates, in particular di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), dipropyl. Heptyl phthalate (DPHP) and diisodecyl phthalate (DIDP) are used, but the terephthalic acid derivative di-2-ethylhexyl terephthalate (DEHT or DOTP) is also used.
At the same time, the production of C10 oxo alcohols, in particular 2-propylheptanol, has risen markedly over the last few years due to the particularly advantageous raw material base, and it can be expected to pursue further improvements in production capacity. The use of said alcohols as starting material for plasticizers is actually limited almost exclusively to the corresponding DIDP or DPHP. The use is in fact included in so-called standard plasticizers, but due to its technical properties of use, in the plastisol market, which is relatively important compared to DEHP, DINP and DOTP, slight gelation and poor plastic properties Can only be used due to significant limitations. Thus, esters of isodecanol having such properties, preferably said swell of isodecanol having a high 2-propylheptanol content, are used in classical thermoplastic applications such as sheets, cable jackets and partially roofing materials. It is desired that more and more plastisol applications may be used with membranes.

  Due to the limited availability of fossil raw materials, the associated future significant price increases and the use of renewed raw materials, which are always strongly required politically, in particular at least the acid component is naturally derived Established resources, such as sugar, fat or oil based esters, should have good market opportunities in the future.

  T. T. et al. Werpy and G.W. In the Petersen publication “Top Value Added Chemicals from Biomass”, 2,5-furandicarboxylic acid (FDCA) is regarded as one of the most promising platelet-like chemicals based on sugar. Due to the structural similarity to terephthalic acid, many books have recently been published regarding the use of 2,5-furandicarboxylic acid or various derivatives primarily in polymers. The main applications are in many cases to replace terephthalic acid or its derivatives partially or completely in the polymer.

  A very extensive overview of FDCA, its uses and possibilities is published on the Internet, Jaroslaw Lewkowski, ARKIVOC 2001 (i), pp. 17-54, ISSN 1414-6376, titled “Synthesis, Chemistry and Applications 5- found in the publication "Hydroxymethylfurfural and it's derivatives". Most of the syntheses are in common to convert carbohydrates, in particular glucose or fructose, preferably fructose, into acid-catalyzed 5-hydroxymethylfurfural (5-HMF), which 5-hydroxymethylfurfural (5 -HMF) can be separated from the reaction medium by process engineering operations, for example in a two-phase mode of operation. Corresponding results were described, for example, by Roman-Leshkov et al. In Science 2006, 312, pages 1933 to 1937, and by Zhang in Angelwandte Chemie 2008, 120, pages 9485-0488.

  Next, in one further step, 5-HMF can be oxidized to FDCA, as cited, for example, by Christensen in ChemSusChem 2007, 1, pages 75-78.

  In addition, the preparation of certain FDCA esters by synthesis starting from mucoic acid (in Tagouchi, Chemistry Letter Vol. 37, No. 1 (2008)) and the corresponding alcohols are also described.

  Heretofore, the use of esters of 2,5-furandicarboxylic acid as plasticizers for plastics, in particular PVC, PVB, PLA, PHB or PAMA, has been described only rarely. The most extensive overview in this regard is R.R. D. Sanderson et al., Journal of Appl. Pol. Sei. 1994, Vol. 53, pages 1785 to 1793. There are explicitly described corresponding esters based on n-butanol, n-hexanol, 2-octanol and 2-ethylhexanol. Tests on the interaction between the ester and PVC have shown that this ester can be used sufficiently as a plasticizer for PVC. However, this conclusion was derived solely from DMTA measurements. No in-use technical tests that are important to the processor and have testimony were conducted.

  Thus, starting from the state of the art, esters based on isodecanol, in particular isodecanol having a high 2-propylheptanol content and an acid component based on renewal raw materials, such as plastics, for example PVC, PVB, It was to provide an ester that can be used as a plasticizer for PLA, PHB or PAMA, and that shows the gelling and plasticizing action of plastisols, which is clearly improved compared to DPHP. It will therefore clearly expand the use spectrum of the underlying alcohol.

  Mixtures of isomeric decyl esters of 2,5-furandicarboxylic acid (formula I) can be used as plasticizers for plastics, in particular PVC, PVB and PAMA, and are already known in the publication It has been found that it exhibits favorable properties compared to esters. Furthermore, this ester likewise exhibits technical advantages in use compared to the corresponding phthalate esters, such as DIDP or DPHP.

  The subject of the invention is thereby a mixture of isomeric decyl esters of 2,5-furandicarboxylic acid of the formula I. Furthermore, the subject of the present invention is a composition containing a mixture of isomeric decyl esters of 2,5-furandicarboxylic acid of the formula I.

  Furthermore, the subject of the present invention is as a solvent, as a plasticizer in plastics or plastic components, in dyes, inks or paints, in plastisols, adhesives or adhesive components, in sealing compounds. A PVC composition or plastisol containing, as a lubricating oil component and as an aid in metalworking, and 5 to 250 parts by weight of the mixture according to the invention per 100 parts by weight of PVC and PVC.

  Furthermore, the object of the present invention is to esterify 2,5-furandicarboxylic acid with a mixture of isomeric decanols, hereinafter referred to as isodecanol, optionally in the presence of a catalyst, or dimethyl 2,5-furandicarboxylic acid. The ester of 2,5-furandicarboxylic acid, characterized in that the ester is transesterified to a mixture of isomeric decyl esters of 2,5-furandicarboxylic acid, optionally using a catalyst, with the liberation of methanol with isodecanol. This is a method for producing a mixture of isomeric decyl esters. Furthermore, the ester mixture according to the invention first converts 2,5-furandicarboxylic acid into a dichloride using a chlorinating agent, which is then reacted under the liberation of isodecanol and hydrogen chloride to give the desired product. It may be obtained by changing.

  Furthermore, for the preparation of a mixture of isomeric decyl esters, it is possible to start with a mucoic acid, which in the presence of isodecanol is preferably cyclized simultaneously within the range of a single tank reaction, preferably under acid catalysis. And converted to the corresponding furandicarboxylic acid diester.

  The mixtures according to the invention of isomeric decyl esters of FDCA have clearly improved properties when used as plasticizers in plastics, in particular PVC, compared to the prior art furandicarboxylic acid esters.

  The esters according to the invention have an improved plasticization effect (efficiency) compared to known DPHP from the state of the art, at least clearly improved gelation on comparable volatility. Compared to a conventional standard product for plastisol applications, DINP, a comparable plasticizing action, only slightly delayed gelling and improved volatility are observed. Compared to DOTP, which is used for several hours based on the discussion of phthalates, the esters according to the invention show an improvement during the gelling and plasticizing action.

In particular, the mixtures according to the invention of isomeric decyl esters of 2,5-furandicarboxylic acid according to formula I are configured such that the mixture of esters has a high proportion of 2-propylheptyl groups . It is preferred that the mixture of esters has a proportion of 2-propylheptyl groups in the C10 side chain in the range from 50 mol% up to 99 mol%. Furthermore, it is preferred that the mixtures according to the invention of the esters have less than 20 mol% of C10 side chains with quaternary C atoms.

  The mixtures according to the invention can consist exclusively of diesters of the formula I or can have at least one polymer and / or at least one plasticizer that is not a diester of the formula I with this diester. The plasticizer may be, for example, citric acid trialkyl ester, acylated citric acid trialkyl ester, glycerin ester, glycol dibenzoate, alkyl benzoate, dialkyl adipate, trialkyl trimellitate, dialkyl terephthalate, dialkyl phthalate, or 1, It may be selected from dialkyl esters of 2-, 1,3- or 1,4-cyclohexanedicarboxylic acid, in which case this alkyl group has 4 to 13, in particular 5, 6, 7, 8, 9, 10, It has 11 or 13 carbon atoms. The plasticizer may be a dianhydrohexitol ester, preferably an isosorbide diester of a carboxylic acid such as n-butyric acid or isobutyric acid, valeric acid or 2-ethylhexanoic acid or isononanoic acid.

  Polymers that may be contained in the mixture according to the invention are, for example, polyvinyl chloride (PVC), polyvinyl butyral (PVB), polylactic acid (PLA), polyhydroxybutyral (PHB) and polyalkyl methacrylate (PAMA). The polymer polyvinyl chloride (PVC) is particularly preferred.

In preferred mixtures with diesters and polymers of formula I, the weight ratio of the singular diester / multiple diester Le polymer / multiple polymer to formula I of the singular, 30: 1 to 1: 2.5, preferably 20: 1-1: 2.

In preferred mixtures having diesters of formula I and plasticizers which are not diesters of formula I, plasticizers, in particular alkyl benzoates, dialkyl adipates, glycerin esters, citric acid trialkyl esters, acylated citric acid trialkyl esters, trialkyl triesters. Melitate, glycol dibenzoate, dialkyl terephthalate, dialkyl phthalate, dialkanoyl ester of isosorbide and / or dialkyl ester of 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid vs. diester of formula I / plural the molar ratio of the diester Le of, 1: 15-15: 1, preferably from 1: 6 to 6: 1.

  The mixtures according to the invention of diesters of formula I or the diesters of formula I themselves may be prepared in various ways.

  In particular, mixtures of diesters of formula I or diesters of formula I are prepared in the manner described below.

  The process according to the invention for preparing the isomeric decyl ester of 2,5-furandicarboxylic acid is a mixture of decanols of 2,5-furandicarboxylic acid or short-chain dialkyl esters of this compound, in particular the dimethyl ester is isomeric. And optionally reacted using a catalyst. Furthermore, 2,5-furandicarboxylic acid dichloride obtainable by reaction of FDCA with a chlorinating agent such as thionyl chloride may be used as a starting material for the preparation of diisodecyl ester. Suitable conditions for converting FDCA through an intermediate step to diisodecyl ester can be found in the examples.

  In particular, mixtures of isomeric decanols having 50 to 99 mol% 2-propylheptanol, in particular 70 to 99 mol%, particularly preferably 85 to 99 mol%, in particular 95 to 99 mol%, are used.

Preparation of isomeric decyl alcohols In principle, all industrial mixtures of decanols, in particular primary alcohols or alcohol mixtures having the general summation formula C ₁₀ H ₂₁ OH, may be used. In particular, the formula C ₉ H ₁₉ CH ₂ as in the above range in relation to the proportion of 2-propylheptanol or n-decanol and the content of polysubstituted C10 alcohols with quaternary C atoms. A mixture of isomeric decanols with OH is used. Decanol having a high proportion of 2-propylheptanol is particularly preferred.

  C10 alcohols which can be used for the preparation of ester mixtures according to the invention are industrially simple C5 aldehydes n-valeraldehyde (= n-pentanal), isovaleraldehyde (2-methylbutanal) and 3-methylbutanal. It can be obtained by aldol condensation followed by dehydrogenation and hydrogenation.

  Also, n-valeraldehyde or isovaleraldehyde may be produced, for example, by hydroformylating 1-butene or 2-butene. In this reaction, n-valeraldehyde and isovaleraldehyde occur at rates that vary depending on the hydroformylation catalyst used and the reaction conditions. When such a mixture is subjected to aldol condensation, various substituted products are obtained, and 3-methylbutanal is obtained by hydroformylation of isobutene.

Isodecanol can be synthesized by the following steps:
a) The C ₄ olefin or C ₄ olefin mixture is hydroformylated to the corresponding C ₅ aldehyde.
b) The aldehyde produced in a) is aldol condensed to decenal.
c) The decenal produced in step b) is hydrogenated to decanol.

  For the production of decanol mixtures, 1-butene, 2-butene, isobutene or mixtures of these olefins are used as starting materials. Hydroformylation of the mixture may be performed by various methods.

  In general, for hydroformylation, cobalt or rhodium catalysts are used unmodified or modified.

  Hydroformylation of isobutene to 3-methylbutanal is described, for example, in the following publications (VY Gankin, LS Genender, DM Rudkovskii, ESSR Zh. Prikl. Khim: (Leningrad) (1968), 41 (10), pp. 2275-2281).

  Hydroformylation of linear butenes or mixtures thereof is disclosed, for example, in EP 0094456, DE 19617178, EP 0562451 or EP 0646563. ing.

n- valeraldehyde, isovaleraldehyde, mixtures of 3-methylbutanal or C ₅ aldehydes, usually as a catalyst aldol condensation under the action of a basic catalyst, alkali metal carbonates or alkali metal hydroxides, Koto In addition, sodium or potassium compounds or amines, in particular tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine are used. It is operated at a temperature of 60 to 160 ° C., in particular 80 to 130 ° C., and a pressure increased to normal pressure or about 1 MPa. The reaction time is from a few minutes to several hours, depending in particular on the catalyst type and the reaction temperature.

Aldol condensation of C ₅ aldehydes in the agitation type reactor is described, for example, in WO 93/20034. The practice of aldol condensation of aldehydes in a tubular reactor is disclosed, for example, in German Patent DE 199 75 522.

Decenal acquired by aldol condensation of C ₅ aldehydes are hydrogenated as in pure form, or mixtures thereof. Hydrogenation is preferably carried out in the liquid phase.

  For hydrogenation, a catalyst or catalyst system that hydrogenates olefinic double bonds as well as carbonyl groups may be used. For the hydrogenation of α, β-unsaturated aldehydes, in particular the catalysts used in the technology for hydrogenation of 2-ethylhex-2-enal to 2-ethylhexanol are suitable.

  For the hydrogenation, for example, copper / nickel catalysts, copper / chromium catalysts, copper / chromium / nickel catalysts, zinc / chromium catalysts, nickel / molybdenum catalysts may be used. A combination of two or more catalysts may be used. The catalyst may be support-free or the hydrogenation active substance or precursors thereof may be applied on a support such as silicon dioxide or aluminum dioxide.

  Preferred catalysts for hydrogenating α, β-unsaturated aldehydes contain 0.3 to 15% by weight of copper and nickel, respectively, on a support material, in particular aluminum oxide and silicon dioxide, and chromium as an activator. 0.5 to 3.5% by weight, and preferably 0.01 to 1.6% by weight, in particular 0.02 to 1.2% by weight, of an alkali component. The quantity descriptions are for a catalyst that has not yet been reduced. The alkaline component is optional.

  The catalyst is advantageously used in a form that results in low flow resistance, for example in the form of granules, pellets or shaped bodies, such as tablets, cylinders, rod extrudates or annular bodies. The catalyst is advantageously activated before use, for example by heating in a stream of hydrogen.

  Hydrogenation, preferably liquid phase hydrogenation, is generally carried out under a total pressure of 0.5 to 20 MPa, in particular 0.5 to 3.0 MPa, particularly preferably 1.5 to 2.5 MPa. Hydrogenation in the gas phase may be carried out at lower pressures, but with a correspondingly large gas volume. If multiple hydrogenation reactors are used, their total pressure in the individual reactors may be the same or different within the aforementioned pressure range.

  The reaction temperature is generally 120 to 220 ° C., in particular 140 to 180 ° C. in the liquid or gaseous phase during the hydrogenation.

  Examples for such hydrogenation are described in EP 0470344 and EP 0326674.

  In some cases, the hydrogenation of decenal to decanol may be carried out in two stages. In this case, the olefinic double bond is hydrogenated, for example with a palladium catalyst, in the first stage, and the carbonyl group is hydrogenated with one of the above catalysts in the second stage.

Starting from a C ₄ olefin, a decanol mixture is produced containing essentially one or more of the following materials:
2-propylheptanol, 4-methyl-2-propyl-hexanol, 5-methyl-2-propyl-hexanol, 2-isopropyl-4-methyl-hexanol, 2-isopropyl-5-methyl-hexanol. The listed decanols each consist of at least two stereoisomers.

The composition of the decanol mixture depends on the raw materials and the hydroformylation process as described above. All decanol mixture is obtained by the method described from C ₄ olefins may be used in the preparation of the esters according to the invention. A particularly preferred decanol mixture consists of 50 to 99 mol% 2-propylheptanol, in particular 70 to 99 mol%, particularly preferably 85 to 99 mol%, in particular 95 to 99 mol%.

Synthesis of isodecyl alcohol from C ₄ olefins or C ₄ olefin mixtures generally trimerizes propylene, followed by hydroformylation, and hydrogenation, resulting in a predominantly methyl branched isodecanol mixture It is more economical than ordinary law. According to another alternative method, C9 alcohols and C11 induced by using olefin mixtures having essentially 8 to 10 C atoms as starting products for hydroformylation together with C10 content The use of a C10 alcohol mixture by a polygas process containing alcohol is also mentioned. Nevertheless, this isodecanol mixture is also suitable for the preparation of the esters according to the invention.

  In this case, by way of example, an isodecanol mixture from ExxonMobil with the commercial name Exxal 10 is mentioned. Furthermore, mixtures of the above variants for preparing the esters according to the invention may be used.

Preferably, mixtures of isomeric decyl alcohols used in the process according to the invention, in particular those having the formula C ₉ H ₁₉ CH ₂ OH, contain less than 20 mol% of decyl alcohol with quaternary C atoms, in particular 10 It contains less than mol%, preferably less than 5 mol%. The presence of this alcohol degrades many use technical properties and also reduces the rate of biological degradation of the molecule.

Furthermore, the isodecanol used in the preparation of the diester of the formula I contained in the mixture according to the invention is preferably of the formula C ₉ H ₁₉ CH ₂ OH with 1-60%, in particular 1-50%, of n-decanol. , Preferably 2-30%. Thereby, a number of technical properties of use, such as gelation, plasticizing action, etc., can be improved, but this alcohol is not formed by aldol condensation of C5 aldehyde and subsequent hydrogenation, and hydroformylation And, if necessary, n-decanol had to be incorporated because it was not formed in an effective content by hydrogenation of the trimer propylene or nonene mixture from the polygas process. N-decanol can again be obtained, for example, industrially by ethylene oligomerization, or by fractionation of fatty alcohols.

  The isomeric distribution of the isomeric alcohols in the mixture is calculated by a method commonly used by those skilled in the art, for example NMR spectroscopy, GC- or GC / MS spectroscopy, preferably after the transition to silyl ester or methyl ester. May be.

Furandicarboxylic acid Furan-2,5-dicarboxylic acid (FDCA, CAS-No. 3238-40-2) has heretofore been unusable on a large industrial scale, but is produced according to the description in the publication. Or can be obtained commercially. The transition to dichloride, which is sometimes desirable or preferred, is described in detail in the examples.

Esterification To produce the esters according to the invention, 2,5-furandicarboxylic acid or a reactive derivative such as the corresponding dichloride (see Examples) is reacted with a mixture of isomeric decanols. Preferably, the esterification is carried out using a catalyst starting from furandicarboxylic acid and isodecanol.

  Esterification of furandicarboxylic acid to the corresponding ester using an isodecanol mixture may be carried out autocatalytically or catalytically, for example using a Bronsted acid or a Lewis acid. Depending on how the type of catalysis is selected, there is always exactly a temperature-dependent equilibrium between the raw material (acid and alcohol) and the product (ester and water). An entraining agent can be used to make the transition to an ester advantageous, which removes the water of reaction from the batch volume. Since the alcohol mixture used for esterification is lower than furan carboxylic acid which boils the reactive derivative and its ester and has a mixing gap with water, this alcohol mixture is often used as an entrainer, and this The entraining agent can be returned to the process again after dehydration.

  The alcohol used for the formation of the ester or the isomeric decanol mixture used simultaneously as entrainer is preferably in excess of the amount required for the formation of the ester, preferably 5 to 50% by weight, in particular 10 to 10%. Used at 30% by weight.

As the esterification catalyst, an acid such as sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid or a metal or a compound thereof can be used. For example, tin, titanium, zirconium are suitable, which are used as finely divided metals or preferably in the form of their salts, oxides or soluble organic compounds. Metallic catalysts, unlike protic acids, are high temperature catalysts whose full activity is first achieved at temperatures above 180 ° C. In this case, however, furandicarboxylic acid has a tendency to decompose CO ₂ at temperatures above 190 ° C., from which further monocarboxylic acids are formed, which are of course no longer It should be noted that it cannot be converted to the target product.

  However, metal catalysts are advantageously used. This is because the metal catalyst forms a few by-products, such as olefins, from the alcohol used in the catalytic reaction compared to protons. Illustrative representative examples for metal catalysts are tin powder, tin (II) oxide, tin (II) oxalate, titanates such as tetraisopropyl orthotitanate or tetrabutyl orthotitanate and zirconium esters such as tetrabutyl zirconate. It is.

  The concentration of the catalyst depends on the type of catalyst. In the case of titanium compounds which are preferably used, this titanium compound is preferably 0.005 to 2.0% by weight, in particular 0.01 to 0.5% by weight, particularly preferably 0.01 to 0.5%, based on the reaction mixture. 0.1% by mass.

  The reaction temperature is 160 ° C. to 270 ° C., in particular 160 to 200 ° C., when using the titanium catalyst. The optimum temperature depends on the feedstock, reaction course and catalyst concentration. This temperature can easily be calculated by testing for each individual case. Even higher temperatures increase the reaction rate and promote side reactions such as dehydration from alcohols or the formation of colored by-products. For the removal of the reaction water, it is advantageous that the alcohol can be distilled off from the reaction mixture. The desired temperature or the desired temperature range can be adjusted by the pressure in the reaction vessel. Thus, in the case of low boiling alcohols, the reaction is carried out at overpressure and in the case of high boiling alcohols is carried out under reduced pressure. For example, when FDCA is reacted with a mixture of isomeric decanols, it is operated within a temperature range of 160 ° C. to 190 ° C. and a pressure range of 0.1 MPa to 0.001 MPa.

  The amount of liquid to be returned during the reaction may consist partly or completely of alcohol obtained by post-treatment of the azeotropic distillate. Post-treatment may also be performed at a later point in time, and the amount of liquid removed may be completely or partially renewed from fresh alcohol, i.e. from alcohol prepared in a storage container. It may be replaced by an alcohol.

  The crude ester mixture containing alcohol, catalyst or its secondary products and optionally by-products together with one or more esters is worked up by methods known per se. In this case, the work-up comprises the following steps: separation of excess alcohol and possibly low boilers, neutralization of the acids present, optionally steam distillation, converting the catalyst into a readily filterable residue. That, separation of the solid, and optionally drying. In this case, depending on the post-treatment method used, the order of these steps may be different.

  In some cases, the mixture of diisodecyl esters comprising the reaction mixture may optionally be separated by distillation after neutralization of the batch amount.

Transesterification According to another alternative method, the diisodecyl ester according to the invention can be obtained by transesterification of furan-2,5-dicarboxylic acid diester with an isodecanol mixture. As the reactant, a furan-2,5-dicarboxylic acid diester in which the alkyl group bonded on the O atom of the ester group has 1 to 9 C atoms is used. Said group may be aliphatic, linear or branched, alicyclic or aromatic. One or more methylene groups of the alkyl group may be substituted with oxygen. It is preferred that the alcohol based on the reactant ester boils at a lower temperature than the isodecanol mixture used. A preferred raw material is furan-2,5-dicarboxylic acid dimethyl ester.

  The transesterification is carried out catalytically, for example using a Bronsted acid or a Lewis acid or base. Depending on how the catalyst is used, there is always exactly a temperature-dependent equilibrium between the raw material (dialkyl ester and isononanol mixture) and the product (diisodecyl ester mixture and free alcohol). In order for the transition to a diisodecyl ester mixture to be advantageous, the alcohol resulting from the reactant ester is distilled off from the reaction mixture.

  Again, it is advantageous to use an excess of the isodecanol mixture. As the transesterification catalyst, an acid such as sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid or a metal or a compound thereof can be used. For example, tin, titanium, zirconium are suitable, which are used as finely divided metals or preferably in the form of their salts, oxides or soluble organic compounds. Metallic catalysts, unlike protic acids, are high temperature catalysts whose full activity is first achieved at temperatures above 180 ° C. However, metal catalysts are advantageously used. This is because the metal catalyst forms a few by-products, such as olefins, from the alcohol used in the catalytic reaction compared to protons. Illustrative representative examples for metal catalysts are tin powder, tin (II) oxide, tin (II) oxalate, titanates such as tetraisopropyl orthotitanate or tetrabutyl orthotitanate and zirconium esters such as tetrabutyl zirconate. It is.

  In addition, basic catalysts such as alkali metal or alkaline earth metal oxides, hydroxides, bicarbonates, carbonates or alcoholates may be used. From this group, preference is given to using alcoholates, such as sodium methylate. The alcoholate may be made in-situ from an alkali metal and decanol or isodecanol mixture.

  The concentration of the catalyst depends on the type of catalyst. The concentration of the catalyst is usually 0.005 to 2.0% by mass with respect to the reaction mixture.

  The reaction temperature for transesterification is usually 100 to 220 ° C. The reaction temperature must be at least high enough to allow the alcohol resulting from the reactant ester to be distilled from the reaction mixture at a defined pressure, often atmospheric pressure.

  The transesterification mixture can be worked up exactly as described for the esterification mixture.

Uses Mixtures according to the invention of isomeric decyl esters of 2,5-furandicarboxylic acid are used as plasticizers, in particular plastic compositions, adhesives, sealing compounds, paints, dyes, plastisols, artificial leather, fiber floor finishes It may be used in materials, under sealants, coated fabrics, wallpaper or inks. In particular, the plasticizer according to the present invention can be used for deformed profiles, sealing materials, food packaging materials, sheets, toys, pharmaceutical products, membranes for roofing materials, artificial leather, textile flooring materials, under sealants, coated fabrics, wallpaper. Used in cable and wire jackets, particularly preferably in food packaging, toys, pharmaceutical products, such as bags and tubes for infusion, dialysis and drainage, wallpaper, textile floor coverings and coated textiles It's okay.

  Using the mixtures according to the invention of the isomeric decyl esters of 2,5-furandicarboxylic acid, compositions according to the invention are obtained which in particular contain a mixture of the isomeric decyl esters of 2,5-furandicarboxylic acid.

  Such a composition can have a mixture according to the invention of the isomeric decyl ester of 2,5-furandicarboxylic acid alone or in a mixture with another plasticizer. If the composition according to the invention comprises a mixture according to the invention of an isomeric decyl ester of 2,5-furandicarboxylic acid in a mixture with another plasticizer, the other plasticizer is in particular a dialkyl phthalate, preferably Phthalic acid dialkyl esters and trimellitic acid trialkyl esters having 4 to 13 C atoms in the alkyl chain, preferably trimellitic acid trialkyl esters having 4 to 10 C atoms in the side chain, respectively, Dialkyl esters of adipic acid having 4 to 13 C atoms in the side chain and preferably dialkyl esters of terephthalic acid; each having 4 to 13 carbon atoms in the side chain, 1,2 having an alkyl = alkyl group -Cyclohexanedioic acid alkyl ester, 1,3-cyclohexanedioic acid alkyl ester and 1,4-cyclohexa Diacid alkyl esters, preferably 1,2-cyclohexane diacid alkyl esters; glycol dibenzoates; alkyl sulfonic acid esters of phenols having 8 to 22 C atoms, especially alkyl groups; especially in alkyl groups Can be selected from the group of polymer plasticizers, glycerin esters, isosorbide esters and alkyl benzoates having 7 to 13 C atoms. In all cases, the alkyl groups are straight or branched and may be the same or different. Particularly preferably, the composition comprises a mixture of isomeric nonyl esters of 2,5-furandicarboxylic acid, in particular benzoic acid alkyl esters having an alkyl = alkyl group, especially having from 7 to 13 carbon atoms. It has benzoic acid isononyl ester, benzoic acid nonyl ester, benzoic acid isodecyl ester, benzoic acid propylheptyl ester or benzoic acid decyl ester. The content of the isomer nonyl ester of 2,5-furandicarboxylic acid in the mixture with another plasticizer is in particular 15 to 90% by weight, particularly preferably 20 to 80% by weight, particularly preferably. 30 to 70% by weight, in which case the total mass of plasticizer present is 100%.

  The described composition consisting of a mixture of isomeric decyl esters of 2,5-furandicarboxylic acid and another plasticizer comprises a plastic composition, an adhesive, a sealing compound, a paint, a dye, It may be used in plastisol or ink.

  The plastic products produced from the plasticizer composition according to the invention can be, for example, the following: profiled profiles, sealing materials, food packaging materials, sheets, toys, pharmaceutical products such as injection, dialysis And roofing membranes, artificial leather, textile floor coverings, undersealants, coated fabrics, wallpaper, cables and wire jackets. Preference is given to food packaging materials, toys, pharmaceutical products, wallpaper, coated textiles and fiber floor finishes.

  A composition according to the invention containing a mixture of isomers of 2,5-furandicarboxylic acid is obtained from polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyacrylates, in particular polymethyl methacrylate (PMMA), Alkyl methacrylate (PAMA), fluoropolymers, especially polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetal, especially polyvinyl butyral (PVB) Polystyrene polymers, especially polystyrene (PS), expandable polystyrene (EPS), acrylonitrile-styrene-acrylate (ASA), styrene acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS), styrene -Maleic anhydride copolymer (SMA), styrene-methacrylic acid copolymer, polyolefin, especially polyethylene (PE) or polypropylene (PP), thermoplastic polyolefin (TPO), polyethylene-vinyl acetate (EVA), polycarbonate, polyethylene terephthalate ( PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), thermoplastic polyurethane (TPU), polysulfide (PSu), biopolymer, especially Polylactic acid (PLA), polyhydroxybutyral (PHB), polyhydroxyvaleric acid (PHV), polyester, starch, cellulose and cellulose derivatives, especially nitrocellulose (N ), Ethyl cellulose (EC), cellulose acetate (CA), cellulose - may have acetate / butyrate (CAB), mixtures or copolymers or polymer selected from those monomer units of rubber or silicone, as well as the polymers described. In particular, the composition according to the invention is a branched chain having 1 to 10 carbon atoms bonded to oxygen atoms of ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, methacrylate, acrylate, ester groups. Or an acrylate or methacrylate having an alkyl ester of an unbranched alcohol, styrene, acrylonitrile or a cyclic olefin.

  Advantageously, the composition according to the invention contains, as PVC type, suspension type PVC, bulk type PVC, fine suspension type PVC or emulsion type PVC. The composition according to the invention contains a plasticizer, in particular 5 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of polymer.

  The composition according to the invention comprises, together with the components described, further components, in particular other plasticizers, fillers, pigments, stabilizers, co-stabilizers such as epoxidized soybean oil and lubricants, foaming agents, degradation promoting agents May contain agents, antioxidants or biocides.

  Compositions with the described polymers may be used as adhesives, seal compounds, paints, dyes, plastisols, artificial leather, textile floor coverings, undersealants, coated fabrics, wallpaper or inks, or these May be used for the manufacture of As long as the composition described is a plastic, this plastic is in particular a profile, a seal, a one-piece or multi-piece fixing device, a food packaging material, a sheet, a toy, a pharmaceutical product, It may be processed into roofing membranes, artificial leather, textile floor coverings, undersealants, coated fabrics, wallpaper, cables and wire jackets.

  The following examples illustrate the invention but do not limit the scope of application of the invention which results from the description and the claims.

Examples Esters according to the invention were initially prepared via dichloride starting from furan-2,5-dicarboxylic acid in a two-step synthesis.

Example 1: Synthesis specification for furan-2,5-dicarboxylic acid dichloride (II) 72 furan-2,5-dicarboxylic acid 72 in a 250 ml three-necked flask equipped with a reflux condenser and dropping funnel under argon atmosphere .1 g (462 mmol) was pre-charged. Over 10 minutes, 165 g (1.39 mol) of thionyl chloride with a few drops of N, N-dimethylformamide added. The suspension was heated to reflux temperature and the resulting gas was passed through a wash bottle with an aqueous KOH solution. The mixture was further heated at reflux for 4 hours until gas evolution ceased and the solid was completely dissolved.

  The product was isolated by purification by distillation after discharge of excess thionyl chloride (T = 110 ° C., p = 0.0012 MPa).

  In this case, 79.4 g of dichloride were produced as a colorless crystalline solid having a melting point of 79.5-80.0 ° C. (89% yield).

  Furan-2,5-dicarboxylic acid dichloride is stored at room temperature in the dark under protective gas (argon) until further use.

Example 2: Synthesis of furan-2,5-dicarboxylic acid ester In a three-necked flask equipped with a reflux condenser and a dropping funnel, dichloride was pre-charged under an argon atmosphere and melted by heating. 2,4 equivalents of alcohol were gradually added dropwise to the liquid, and an exothermic reaction occurred with the generation of gas. The resulting gas was passed through a wash bottle with an aqueous KOH solution. After the conversion was complete, the mixture was stirred at a temperature of 80 to 100 ° C. for 16 hours.

  Excess alcohol was removed under reduced pressure in the presence of zeolite and the crude product was purified by double distillation.

  For the synthesis of the comparative example, commercially available 2-ethylhexanol was used. In order to produce the ester mixture according to the invention, CAS registration no. 10042-59-8 commercially available C10 alcohol is used, for example, this C10 alcohol is provided as propylheptanol.

This last propylheptanol had the following composition by gas chromatography analysis:
2-propylheptanol 85.3% by mass; 2-propyl-4-methylhexanol 13.4% by mass; balance 0.3% by mass.

  In the following Table 1, the results of the two synthesis are recorded.

  Therefore, the conversion of furan-2,5-dicarboxylic acid dichloride (2) into the corresponding ester is almost quantitative.

Example 3: Preparation of plastisols Preferred properties achievable with the esters according to the invention are shown below for plastisols and semi-finished products obtained therefrom.
The weighed amounts of ingredients used for the various plastisols can be ascertained from Table 2 below.

  The liquid component was weighed in a suitable PE cup in front of the solid component. Manually mix the mixture with a paste spatula until there was no longer any wet powder. Next, the mixed beaker was fixed in a tightening device of a dissolver stirrer. The sample was homogenized using a suitable mixing disc. In this case, the number of rotations was increased to 330 rpm to 2000 rpm, and stirring was performed using a thermosensor digital display device until the temperature reached 30.0 ° C. Thereby, it was ensured that homogenization of the plastisol was achieved with the prescribed energy supply. The plastisol was then immediately adjusted to a temperature of 25.0 ° C.

Example 4: Measurement of Gelation Rate Testing of the gelation behavior of plastisol in a vibration mode in Physica MCR 101, operated with controlled shear stress (Platte-Plate System) (PP25) It was performed using. An additional temperature control bonnet was connected to the instrument to achieve optimal heat distribution.

The following parameters were set:
Mode: Temperature gradient start temperature: 25 ° C
Final temperature: 180 ° C
Heating / cooling rate: 5 ° C / min Temperature after measurement: 25 ° C
Vibration frequency: 4 to 0.1 Hz Gradient, logarithmic angular frequency Ω: 10 1 / s
Number of measurement points: 63
Measurement point time: 0.5 minutes Automatic gap compensation F: 0 N
Constant measurement point time gap width: 0.5 mm.

Implementation of measurement:
On the plate below the measuring system, a spatula was used to apply the droplets of the plastisol formulation to be measured free of bubbles. In doing so, it was noted that some plastisol could exude uniformly from the measurement system after closing the measurement system (less than about 6 mm in circumference). Subsequently, the temperature control bonnet was positioned on the sample, and measurement was started.

  The complex viscosity of the so-called plastisol was measured depending on the temperature. The onset of the gelation process should be confirmed at a sudden increase in complex viscosity. The earlier this viscosity increase started, the better the gelling ability of the system. For comparison, the temperature at which a complex viscosity of 1000 Pa · s was achieved was measured from the interpolation curve for each plastisol.

In this case, the values listed in Table 3 were found:

  Here it can be clearly seen that the flange ester (plastisol 1) according to the invention has an improved gelation compared to the corresponding phthalate DPHP (plastisol 4) and terephthalate DOTP (plastisol 5). The large gap in the gelation rate that opens between both phthalates DINP and DPHP is closed by the esters according to the invention.

Example 5: Measurement of Shore Hardness of Cast Product Shore hardness A is one criterion for the softness of the specimen. The more the specified needle can enter the specimen at a given measurement time, the lower the measurement value. The plasticizer with the highest efficiency yields the lowest value for Shore hardness at the same plasticizer amount. Conversely, a very efficient plasticizer can save a certain percentage in the formulation, which often means a cost reduction for the processor.

  In order to measure the Shore hardness, the plastisol produced as described in Example 4 was poured into a circular casting mold having a diameter of 42 mm. The plastisol in the mold was then gelled in an air circulating drying cabinet at 200 ° C. for 30 minutes, removed after cooling and stored in the drying cabinet (25 ° C.) for at least 24 hours before measurement. The disc thickness was about 12 m.

  The measurement itself was carried out according to DIN 53505 using a Shore A measuring device from Zwick-Roell, and the measured value was read after 3 seconds each time. For each specimen, three different measurements were performed at different locations (except for the surrounding area), and the measured values were recorded each time.

  Table 5 lists the measured values obtained.

  The described examples show that the isodecyl ester of furan carboxylic acid is indeed of the same value as DINP and has a clear improvement in plasticizing action compared to the corresponding phthalate DPHP and terephthalate DOTP. Prove that you have.

Example 6: Production of sheet from plastisol In order to produce test specimens, a 1 mm thick sheet was first produced for each formulation from Table 3. For this purpose, first a high-gloss release paper (Sappi, Italy) was cut to a size of 30 × 44 cm and placed on the stretch frame of a coating device LTSV for the Mathis furnace. Thereafter, the tension frame was placed on the guide frame, the Mathis furnace (LTF type) was adjusted to 200 ° C., and after reaching this temperature, the frame was preheated for 15 seconds. Thereafter, the coater was installed in a tensioning device, and the gap of the coater was adjusted by a pre-test so that the thickness of the sheet after completion of gelation was 1 mm (± 0.05 mm). Excess paste was collected by applying an adhesive strip to the front edge of the paper. Thereafter, the paste was applied in front of the coater, and the paste was spread on the release paper stretched by pulling the guide frame together with the coater (speed: about 6 m / min). The coater was then removed and the adhesive strip removed with excess paste. Subsequently, the melting roll was lowered and the tension frame was moved into the furnace. After gelation (200 ° C. for 2 minutes), the frame was removed from the furnace again, and after cooling, the sheet was peeled from the paper.

Example 7: Measurement of volatility from sheet From the sheet produced in Example 6 and having a thickness of about 1 mm, two discs each having an area of 50 cm ² were punched out. This specimen was stored in a desiccator with a dry gel at constant air humidity for at least 24 hours.

  Prior to the start of a series of measurements, a zero specimen was measured. Zero test results were discarded. This is because this measurement was used only for the hot operating phase of the instrument. The conditioned specimens were then positioned in the center on the Einweg Alusture and weighed in a Mettler halogen dryer HB43S. A standard heating program was used for measurements in the halogen dryer. For this, the following parameters were adjusted: the heating rate was adjusted to a maximum of 200 ° C. with a linear gradient. A 10 minute time period was established for the test time. Measurements (time, temperature and mass loss) were automatically transmitted to the evaluation software (Microsoft Excel) using a data cable for a total of 0.5 minutes. At least one duplicate measurement was performed for each specimen. When the measurement result was more than 10%, another measurement was performed. The average value of mass loss is shown in a chart. Next, after each measurement, it waited until the instrument was cooled again below 50 ° C. Thereafter, the next measurement was started immediately.

  Table 5 lists the mass loss after 10 minutes at 200 ° C.

  Sheets made from the esters according to the invention exhibit the least volatility.

  Thereby, it was possible to show that the esters according to the invention outperform DOTP and have a behavior similar to DINP. Accordingly, the above problem of generating additional use potential for isodecanol rich in 2-propylheptanol is developed by developing a plasticizer that is competitive in plastisol compared to DINP and DOTP. I was able to.

Claims (15)

Formula I

A mixture of isomeric decyl esters of furan-2,5-dicarboxylic acid represented by
A mixture of the isomer decyl esters of the furan-2,5-dicarboxylic acid having less than 20 mol% of C10 side chains having quaternary C atoms .   2. An isomeric decyl ester of furan-2,5-dicarboxylic acid according to claim 1, wherein the mixture of esters has a proportion of 2-propylheptyl groups in the C10 side chain in the range of 50 mol% up to 99 mol%. Mixture of. A process for producing a mixture of isomeric decyl esters of furan-2,5-dicarboxylic acid of formula I according to claim 1,
a) contacting furan-2,5-dicarboxylic acid with a mixture of isomeric C10 alcohols under the liberation of water;
b) in which a mixture of isomeric C10 alcohols in molar excess up to 50% is used;
c) performing the reaction described in a) using a catalyst selected from the group of Bronsted acids and / or Lewis acids,
Process for the preparation of a mixture of isomeric decyl esters of furan-2,5-dicarboxylic acid of the formula I. A process for producing a mixture of isomeric decyl esters of furan-2,5-dicarboxylic acid of formula I according to claim 1,
a) converting furan-2,5-dicarboxylic acid into the corresponding furan-2,5-dicarboxylic acid chloride,
b) characterized in that it is subsequently contacted with a mixture of isomeric C10 alcohols under liberation of hydrogen chloride after separation and purification,
Process for the preparation of a mixture of isomeric decyl esters of furan-2,5-dicarboxylic acid of the formula I. A process for producing a mixture of isomeric decyl esters of furan-2,5-dicarboxylic acid of formula I according to claim 1,
a) contacting furan-2,5-dicarboxylic acid dimethyl ester with a mixture of isomeric C10 alcohols under liberation of methanol;
b), characterized in that the reaction described in a) is carried out using a catalyst selected from the group of Bronsted acids and / or Lewis acids,
Process for the preparation of a mixture of isomeric decyl esters of furan-2,5-dicarboxylic acid of the formula I.   Mixtures of isomer decyl esters of furan-2,5-dicarboxylic acid of formula I according to claim 1 and alkyl benzoates, dialkyl adipates, glycerin esters, citric acid trialkyl esters, acylated citric acid trialkyl esters , Trialkyl trimellitate, glycol dibenzoate, dialkyl terephthalate, dialkyl phthalate, dialkanoyl ester of isosorbide and / or dialkyl ester of 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid A composition containing a plasticizer. The composition of claim 6 wherein the ratio of the isomeric decyl ester of furan-2,5-dicarboxylic acid of formula I to the plasticizer is in the range of 1:15 to 15: 1. The composition according to claim 6 or 7 , wherein the composition comprises a polymer selected from polyvinyl chloride, polyvinyl butyral, polylactic acid, polyhydroxybutyral and / or polyalkyl methacrylate.   A mixture of isomeric decyl esters of furan-2,5-dicarboxylic acid of formula I according to claim 1 and a polymer selected from polyvinyl chloride, polyvinyl butyral, polylactic acid, polyhydroxybutyral and / or polyalkylmethacrylate. Containing composition. 10. The composition of claim 9 , wherein the ratio of polymer to isomeric decyl ester of furan-2,5-dicarboxylic acid of formula I is in the range of 30: 1 to 1: 2.5. Use of an isomeric decyl ester of furan-2,5-dicarboxylic acid of the formula I according to claim 1 or 2 as a plasticizer. Dyes, inks, adhesives or adhesive components, paints, plastisols, or in the production of sealing compound, as a plasticizer in plastics or plastic components, according to any one of claims 6 to 10 Use of the composition. Use of the composition according to any one of claims 6 to 10 as a solvent in the production of dyes, inks, adhesives or adhesive components, paints, plastisols or sealing compounds. Use of the composition according to any one of claims 6 to 10 as a lubricating oil component. Use of a composition according to any one of claims 6 to 10 as an aid in metalworking.